Alkyl-Analide Producing Method

ABSTRACT

The present invention relates to a process for preparing known fungicidally effective alkylanilides from acid chlorides and aminoacetophenone via hydroxyalkyl-substituted carboxanilides, alkenylanilides and benzoxazine derivatives.

The present invention relates to a novel process for preparing known fungicidally effective alkylanilides from acid chlorides and aminoacetophenone via hydroxyalkyl-substituted carboxanilides, alkenylanilides and benzoxazine derivatives.

It is already known that alkylanilides are obtained by reacting the desired acid chloride with the corresponding alkylaniline derivative (cf. EP-A 0 824 099, WO 03/010149).

Furthermore, it is known that alkylanilides are obtained when the corresponding alkenyl- or alkinylanilides are hydrogenated, it being possible to obtain the alkenylanilides from acylanilides by reaction with a phosphoric acid compound in a Wittig-like reaction (cf. WO 03/010149).

Thus, the present invention provides a process for preparing alkylanilides of the formula (I)

in which

-   R¹ represents hydrogen or fluorine, -   R² represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl     having 1 to 9 fluorine, chlorine and/or bromine atoms, -   A represents the radical of the formula (A1)

in which

-   R³ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl,     C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,     C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5     halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl, -   R⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy or     C₁-C₄-alkylthio, -   R⁵ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl,     C₂-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl,     C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl,     C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having     in each case 1 to 5 halogen atoms, or phenyl,     or -   A represents the radical of the formula (A2)

in which

-   -   R⁶ and R⁷ independently of one another represent hydrogen,         halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen         atoms,     -   R⁸ represents halogen, cyano or C₁-C₄-alkyl, or C₁-C₄-haloalkyl         or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A3)

in which

-   -   R⁹ and R¹⁰ independently of one another represent hydrogen,         halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen         atoms,     -   R¹¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A4)

in which

-   -   R¹² represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl,         C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having         in each case 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A5)

in which

-   -   R¹³ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl,         C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl,         C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to         halogen atoms,     -   R¹⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl,         C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy         having in each case 1 to 5 halogen atoms, C₁-C₄-alkylsulphinyl         or C₁-C₄-alkylsulphonyl,         or

-   A represents the radical of the formula (A6)

in which

-   -   R¹⁵ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5         halogen atoms,     -   R¹⁶ represents C₁-C₄-alkyl,     -   Q¹ represents S (sulphur), O (oxygen), SO, SO₂ or CH₂,     -   p represents 0, 1 or 2, where R¹⁶ represents identical or         different radicals if p represents 2,         or

-   A represents the radical of the formula (A7)

in which

-   -   R¹⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5         halogen atoms,         or

-   A represents the radical of the formula (A8)

in which

-   -   R¹⁸ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5         halogen atoms,         or

-   A represents the radical of the formula (A9)

in which

-   -   R¹⁹ and R²⁰ independently of one another represent hydrogen,         halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5         halogen atoms,     -   R²¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A 10)

in which

-   -   R²² and R²³ independently of one another represent hydrogen,         halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1         to 5 halogen atoms,     -   R²⁴ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A11)

in which

-   -   R²⁵ represents hydrogen, halogen, amino, C₁-C₄-alkylamino,         di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,     -   R²⁶ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1         to 5 halogen atoms,         or

-   A represents the radical of the formula (A12)

in which

-   -   R²⁷ represents hydrogen, halogen, amino, C₁-C₄-alkylamino,         di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,     -   R²⁸ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1         to 5 halogen atoms,         or

-   A represents the radical of the formula (A13)

in which

-   -   R²⁹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1         to 5 halogen atoms,         or

-   A represents the radical of the formula (A14)

in which

-   -   R³⁰ represents hydrogen or C₁-C₄-alkyl,     -   R³¹ represents halogen or C₁-C₄-alkyl,         or

-   A represents the radical of the formula (A15)

in which

-   -   R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5         halogen atoms,         or

-   A represents the radical of the formula (A 16)

in which

-   -   R³³ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A17)

in which

-   -   R³⁴ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy,         C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or         C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A18)

in which

-   -   R³⁵ represents hydrogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl         having 1 to 5 halogen atoms, C₁-C₄-alkoxy-C₁-C₄-alkyl,         hydroxy-C₁-C₄-alkyl, C₁-C₄-alkylsulphonyl,         di(C₁-C₄-alkyl)aminosulphonyl, C₁-C₆-alkylcarbonyl or in each         case optionally substituted phenylsulphonyl or benzoyl,     -   R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,     -   R³⁷ represents hydrogen, halogen, cyano, C₁-C₄-alkyl or         C₁-C₄-haloalkyl having 1 to 5 halogen atoms,     -   R³⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl         having 1 to 5 halogen atoms,         or

-   A represents the radical of the formula (A19)

in which

-   -   R³⁹ represents C₁-C₄-alkyl,         characterized in that

-   a) in a first step carbonyl halides of the formula (II)

-   -   in which     -   A is as defined above and     -   Hal¹ represents fluorine, chlorine or bromine,     -   are reacted with acetophenone derivatives of the formula (III)         or salts thereof

-   -   in which R¹ is as defined above,     -   if appropriate in the presence of an acid binder and if         appropriate in the presence of a diluent,         and

-   b) the resulting acetylanilides of the formula (IV)

-   -   in which A and R¹ are as defined above,     -   are, in a second step, reacted with a Grignard reagent of the         formula (V)

-   -   in which     -   R² is as defined above and     -   Hal² represents chlorine, bromine or iodine,     -   in the presence of a diluent,         and

-   c) the resulting hydroxyalkylcarboxanilides of the formula (VI)

-   -   in which R¹, R² and A are as defined above,     -   are, in a last step analogously to the fourth step, hydrogenated         in the presence of a catalyst and in the presence of a diluent,     -   or     -   initially, in an alternative third step, reacted in the presence         of an acid and in the presence of a diluent,         and

-   d) the resulting benzoxazines of the formula (VIIa) and     alkenylanilides of the formulae (VIIb) and (VIIc)

-   -   in which R¹, R² and A are as defined above,     -   are, in a fourth step, hydrogenated in the presence of a         catalyst, if appropriate in the presence of an acid and in the         presence of a diluent.

Surprisingly, the alkylanilides of the formula (I) can be prepared under the conditions according to the invention in good yields, with high purity and selectivity. The removal of the bases used by extractive processes, which is difficult owing to the poor solubility of (IV) can be avoided in an advantageous manner when, in a preferred variant of the process, the reaction of the first step is carried out without using a base, where the hydrogen halide liberated is, when the reaction is carried out in the heat, released into the gaseous phase.

In particular the right choice of solvent in the second step of the process according to the invention results in considerably enhanced yields compared to the processes of the prior art. In a preferred variant of step 2 of the process, solid, undissolved (IV) is added to an unpolar solvent, such as toluene, and the Grignard/ether solution is added simultaneously. In this manner, it can be avoided that the poorly soluble (IV) has to be dissolved in the required large amounts of a polar solvent unfavourable for the reaction, which would be necessary according to the prior art. Surprisingly, this is associated with a high increase in yield, since under classical conditions the reaction stops after little (IV) has been converted.

Once the third step has been carried out, unreacted (IV) can be recovered easily by stirring the product with heptane and selective precipitation of (IV).

Surprisingly, the third step (elimination of water) yields preferably the oxazine of the general formula (VIIa) in the case of short reaction times, whereas in the case of relatively long reaction times and using other water-limiting reagents, the preferred formation of the alkenylanilides (VIIb) and (VIIc) is observed. These in turn can be hydrogenated under milder conditions.

On the other hand, it is also possible to reduce hydroxyalkylcarboxanilides of the formula (VI) directly, without separate elimination of water.

Using, for example, 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl chloride and 2-aminoacetophenone as starting materials, the process according to the invention can be illustrated by the formula scheme below:

The formula (II) provides a general definition of the carbonyl halides used as starting materials for carrying out the process according to the invention. Hal¹ preferably represents fluorine or chlorine. The substituent A has the meanings A1 to A19 given above.

-   A preferably represents one of the radicals A1, A2, A3, A4, A5, A6,     A9, A10, A11, A12, A16, A17 or A18. -   A particularly preferably represents one of the radicals A1, A2, A3,     A4, A5, A6, A9, A11, A16, A17, A18. -   A very particularly preferably represents the radical A1. -   A furthermore very particularly preferably represents the radical     A2. -   A furthermore very particularly preferably represents the radical     A3. -   A furthermore very particularly preferably represents the radical     A4. -   A furthermore very particularly preferably represents the radical     A5. -   A furthermore very particularly preferably represents the radical     A6. -   A furthermore very particularly preferably represents the radical     A9. -   A furthermore very particularly preferably represents the radical     A11. -   A furthermore very particularly preferably represents the radical     A16. -   A furthermore very particularly preferably represents the radical     A17. -   A furthermore very particularly preferably represents the radical     A18.

In the radicals A1 to A19, the substituents given above have the preferred meanings below.

-   R³ preferably represents hydrogen, cyano, fluorine, chlorine,     bromine, iodine, methyl, ethyl, isopropyl, methoxy, ethoxy,     methylthio, ethylthio, cyclopropyl, C₁-C₂-haloalkyl,     C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine     and/or bromine atoms, trifluoromethylthio, difluoromethylthio,     aminocarbonyl, aminocarbonylmethyl or amino-carbonylethyl. -   R³ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, methyl, ethyl, isopropyl, monofluoromethyl,     monofluoroethyl, difluoromethyl, trifluoromethyl,     difluorochloromethyl, trichloromethyl, dichloromethyl, cyclopropyl     methoxy, ethoxy, trifluoromethoxy, trichloromethoxy, methylthio,     ethylthio, trifluoromethylthio or difluoromethylthio. -   R³ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, iodine, methyl, isopropyl, monofluoromethyl,     monofluoroethyl, difluoromethyl, trifluoromethyl,     difluorochloromethyl or trichloromethyl. -   R³ especially preferably represents methyl, difluoromethyl,     trifluoromethyl or 1-fluoroethyl. -   R⁴ preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio. -   R⁴ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine or methyl. -   R⁴ very particularly preferably represents hydrogen, fluorine,     chlorine or methyl. -   R⁵ preferably represents hydrogen, methyl, ethyl, n-propyl,     isopropyl, C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or     bromine atoms, hydroxymethyl, hydroxyethyl, cyclopropyl,     cyclopentyl, cyclohexyl or phenyl. -   R⁵ particularly preferably represents hydrogen, methyl, ethyl,     isopropyl, trifluoromethyl, difluoromethyl, hydroxymethyl,     hydroxyethyl or phenyl. -   R⁵ very particularly preferably represents hydrogen, methyl,     trifluoromethyl or phenyl. -   R⁵ especially preferably represents methyl. -   R⁶ and R⁷ independently of one another preferably represent     hydrogen, fluorine, chlorine, bromine, methyl, ethyl or     C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R⁶ and R⁷ independently of one another particularly preferably     represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,     difluoromethyl, trifluoromethyl, difluorochloromethyl or     trichloromethyl. -   R⁶ and R⁷ independently of one another very particularly preferably     represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,     difluoromethyl, trifluoromethyl or trichloromethyl. -   R⁶ and R⁷ especially preferably each represent hydrogen. -   R⁸ preferably represents fluorine, chlorine, bromine, cyano, methyl,     ethyl, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to     5 fluorine, chlorine and/or bromine atoms. -   R⁸ particularly preferably represents fluorine, chlorine, bromine,     cyano, methyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy,     difluorochloromethoxy or trichloromethoxy. -   R⁸ very particularly preferably represents fluorine, chlorine,     bromine, iodine, methyl, trifluoromethyl or trifluoromethoxy. -   R⁸ especially preferably represents methyl. -   R⁹ and R¹⁰ independently of one another preferably represent     hydrogen, fluorine, chlorine, bromine, methyl, ethyl or     C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R⁹ and R¹⁰ independently of one another particularly preferably     represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,     difluoromethyl, trifluoromethyl, difluorochloromethyl or     tichloromethyl. -   R⁹ and R¹⁰ independently of one another very particularly preferably     represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,     difluoromethyl, trifluoromethyl or trichloromethyl. -   R⁹ and R¹⁰ especially preferably each represent hydrogen. -   R¹¹ preferably represents hydrogen, fluorine, chlorine, bromine,     methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R¹¹ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, methyl or trifluoromethyl. -   R¹¹ very particularly preferably represents methyl. -   R¹² preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₂-haloalkyl,     C₁-C₂-haloalkoxy or C₁-C₂-haloalkylthio having in each case 1 to 5     fluorine, chlorine and/or bromine atoms. -   R¹² particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, hydroxyl, cyano, methyl, ethyl, n-propyl,     isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl,     trifluoromethyl, difluorochloromethyl, trichloromethyl,     trifluoromethoxy, difluoromethoxy, difluorochloromethoxy,     trichloromethoxy, trifluoromethylthio, difluoromethylthio,     difluorochloromethylthio or trichloromethylthio. -   R¹² very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl     or trichloromethyl. -   R¹² especially preferably represents iodine, methyl, difluoromethyl     or trifluoromethyl. -   R¹³ preferably represents fluorine, chlorine, bromine, iodine,     hydroxyl, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio,     ethylthio, difluoromethylthio, trifluoromethylthio, C₁-C₂-haloalkyl     or C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R¹³ particularly preferably represents fluorine, chlorine, bromine,     iodine, hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl,     n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl,     difluoromethyl, difluorochloromethyl, trichloromethyl, methoxy,     ethoxy, methylthio, ethylthio, difluoromethylthio,     trifluoromethylthio, trifluoromethoxy, difluoromethoxy,     difluorochloromethoxy or trichloromethoxy. -   R¹³ very particularly preferably represents fluorine, chlorine,     bromine, iodine, methyl, trifluoromethyl, difluoromethyl or     trichloromethyl. -   R¹⁴ preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, cyano, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,     C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy having in each case 1 to 5     fluorine, chlorine and/or bromine atoms, C₁-C₂-alkylsulphinyl or     C₁-C₂-alkylsulphonyl. -   R¹⁴ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, cyano, n-propyl, isopropyl, n-butyl, isobutyl,     sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,     difluorochloromethyl, trichloromethyl, methoxy, ethoxy, methylthio,     ethylthio, trifluoromethoxy, difluoromethoxy, difluorochloromethoxy,     trichloromethoxy, methyl-sulphinyl or methylsulphonyl. -   R¹⁴ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, iodine, n-propyl, isopropyl, n-butyl, isobutyl,     sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,     trichloromethyl, methylsulphinyl or methylsulphonyl. -   R¹⁴ especially preerably represents hydrogen. -   R¹⁵ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1     to 5 fluorine, chlorine and/or bromine atoms. -   R¹⁵ particularly preferably represents methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R¹⁶ preferably represents methyl or ethyl. -   R¹⁶ particularly preferably represents methyl. -   Q¹ preferably represents S (sulphur), SO₂ or CH₂. -   Q¹ particularly preferably represents S (sulphur) or CH₂. -   Q¹ very particularly preferably represents S (sulphur). -   p preferably represents 0 or 1. -   p particularly preferably represents 0. -   R¹⁷ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1     to 5 fluorine, chlorine and/or bromine atoms. -   R¹⁷ particularly preferably represents methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R¹⁷ very particularly preferably represents methyl, trifluoromethyl,     difluoromethyl or trichloromethyl. -   R¹⁸ preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1     to 5 fluorine, chlorine and/or bromine atoms. -   R¹⁸ particularly preferably represents methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R¹⁸ very particularly preferably represents methyl, trifluoromethyl     difluoromethyl or trichloromethyl. -   R¹⁹ and R²⁰ independently of one another preferably represent     hydrogen, fluorine, chlorine, bromine, amino, methyl, ethyl or     C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R¹⁹ and R²⁰ independently of one another preferably represent     hydrogen, fluorine, chlorine, bromine, methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R¹⁹ and R²⁰ independently of one another very particularly     preferably represent hydrogen, fluorine, chlorine, bromine, methyl,     trifluoromethyl, difluoromethyl or trichloromethyl. -   R¹⁹ and R²⁰ especially preferably each represent hydrogen. -   R²¹ preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine,     chlorine and/or bromine atoms. -   R²¹ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethyl,     difluorochloromethyl or trichloromethyl. -   R²¹ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, methyl, trifluoromethyl, difluoromethyl or     trichloromethyl. -   R²¹ especially preferably represents methyl. -   R²² and R²³ independently of one another preferably represent     hydrogen, fluorine, chlorine, bromine, amino, nitro, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²² and R²³ independently of one another particularly preferably     represent hydrogen, fluorine, chlorine, bromine, nitro, methyl,     ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R²² and R²³ independently of one another very particularly     preferably represent hydrogen, fluorine, chlorine, bromine, methyl,     trifluoromethyl, difluoromethyl or trichloromethyl. -   R²² and R²³ especially prfa each represent hydrogen. -   R²⁴ preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine,     chlorine and/or bromine atoms. -   R²⁴ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethyl,     difluorochloromethyl or trichloromethyl. -   R²⁴ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, methyl, trifluoromethyl, difluoromethyl or     trichloromethyl. -   R²⁴ especially preferably represents methyl. -   R²⁵ preferably represents hydrogen, fluorine, chlorine, bromine,     amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²⁵ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, amino, methyl-amino, dimethylamino, cyano, methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R²⁵ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, amino, methylamino, dimethylamino, methyl,     trifluoromethyl, difluoromethyl or trichloromethyl. -   R²⁵ especially preferably represents amino, methylamino,     dimethylamino, methyl or trifluoromethyl. -   R²⁶ preferably represents fluorine, chlorine, bromine, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²⁶ particularly preferably represents fluorine, chlorine, bromine,     methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl     or trichloromethyl. -   R²⁶ very particularly preferably represents fluorine, chlorine,     bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl. -   R²⁶ especially preferably represents methyl, trifluoromethyl or     difluoromethyl. -   R²⁷ preferably represents hydrogen, fluorine, chlorine, bromine,     amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²⁷ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, amino, methyl-amino, dimethylamino, cyano, methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R²⁷ very particularly preferably represents hydrogen, fluorine,     chlorine, bromine, amino, methylamino, dimethylamino, methyl,     trifluoromethyl, difluoromethyl or trichloromethyl. -   R²⁷ especially preferably represents amino, methylamino,     dimethylamino, methyl or trifluoromethyl. -   R²⁸ preferably represents fluorine, chlorine, bromine, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²⁸ particularly preferably represents fluorine, chlorine, bromine,     methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl     or trichloromethyl. -   R²⁸ very particularly preferably represents fluorine, chlorine,     bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl. -   R²⁸ represents methyl, trifluoromethyl or difluoromethyl. -   R²⁹ preferably represents fluorine, chlorine, bromine, methyl, ethyl     or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine and/or bromine     atoms. -   R²⁹ particularly preferably represents fluorine, chlorine, bromine,     methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl     or trichloromethyl. -   R²⁹ very particularly preferably represents fluorine, chlorine,     bromine, methyl, trifluoromethyl, difluoromethyl or trichloromethyl. -   R³⁰ preferably represents hydrogen, methyl or ethyl. -   R³⁰ particularly preferably represents methyl. -   R³¹ preferably represents fluorine, chlorine, bromine, methyl or     ethyl. -   R³¹ particularly preferably represents fluorine, chlorine or methyl. -   R³² preferably represents methyl, ethyl or C₁-C₂-haloalkyl having 1     to 5 fluorine, chlorine and/or bromine atoms. -   R³² particularly preferably represents methyl, ethyl,     trifluoromethyl, difluoromethyl, difluorochloromethyl or     trichloromethyl. -   R³² very particularly preferably represents methyl, trifluoromethyl,     difluoromethyl or trichloromethyl. -   R³² especially preferably represents methyl or trifluoromethyl. -   R³³ preferably represents hydrogen, fluorine, chlorine, bromine,     methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R³³ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, methyl or trifluoromethyl. -   R³⁴ preferably represents fluorine, chlorine, bromine, iodine,     hydroxyl, C₁-C₄-alkyl, methoxy, ethoxy, methylthio, ethylthio,     difluoromethylthio, trifluoromethylthio, C₁-C₂-haloalkyl or     C₁-C₂-haloalkoxy having in each case 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R³⁴ particularly preferably represents fluorine, chlorine, bromine,     iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,     sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl,     difluorochloromethyl or trichloromethyl. -   R³⁴ very particularly preferably represents fluorine, chlorine,     bromine, iodine, methyl, trifluoromethyl, difluoromethyl or     trichloromethyl. -   R³⁵ preferably represents hydrogen, methyl, ethyl, C₁-C₂-haloalkyl     having 1 to 5 fluorine, chlorine and/or bromine atoms,     C₁-C₂-alkoxy-C₁-C₂-alkyl, hydroxymethyl, hydroxyethyl,     methylsulphonyl or dimethylaminosulphonyl. -   R³⁵ particularly preferably represents hydrogen, methyl, ethyl,     trifluoromethyl, methoxymethyl, ethoxymethyl, hydroxymethyl or     hydroxyethyl. -   R³⁵ very particularly preferably represents methyl or methoxymethyl. -   R³⁶ preferably represents hydrogen, fluorine, chlorine, bromine,     methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R³⁶ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, methyl, ethyl, trifluoromethyl, difluoromethyl or     trichloromethyl. -   R³⁶ very particularly preferably represents hydrogen or methyl. -   R³⁷ preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, cyano, methyl, ethyl, isopropyl or C₁-C₂-haloalkyl having 1     to 5 fluorine, chlorine and/or bromine atoms. -   R³⁷ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, cyano, methyl, ethyl, isopropyl, trifluoromethyl,     difluoromethyl, difluorochloromethyl or trichloromethyl. -   R³⁷ very particularly preferably represents hydrogen, methyl,     difluoromethyl or trifluoromethyl. -   R³⁸ preferably represents hydrogen, fluorine, chlorine, bromine,     methyl, ethyl or C₁-C₂-haloalkyl having 1 to 5 fluorine, chlorine     and/or bromine atoms. -   R³⁸ particularly preferably represents hydrogen, fluorine, chlorine,     bromine, iodine, methyl or trifluoromethyl. -   R³⁸ very particularly preferably represents hydrogen. -   R³⁹ preferably represents methyl, ethyl, n-propyl or isopropyl. -   R³⁹ particularly preferably represents methyl or ethyl.

The general or preferred radical definitions or illustrations given above can be combined between the respective ranges and preferred ranges as desired. They apply both to the end products and to the precursors and intermediates.

The carboxylic acid derivatives of the formula (II) are known and/or can be prepared by known processes (cf. WO 93/11117, EP-A 0 545 099, EP-A 0 589 301 and EP-A 0 589 313).

The formula (III) provides a general definition of the acetophenone derivatives furthermore used as starting materials for carrying out the process according to the invention. In this formula (III), R¹ preferably represents hydrogen. R¹ furthermore preferably represents fluorine.

Acetophenone derivatives of the formula (III) are known (cf. WO 03/010149).

The formula (IV) provides a general definition of the acetylanilides which occur as intermediates when carrying out the process according to the invention. In this formula (IV), A and R¹ have the preferred, particularly preferred, very particularly preferred and especially preferred meanings given above.

Some of the acetylanilides of the formula (IV) are known (cf. WO 03/010149). Acetylanilides of the formula (IV-a)

in which A and R¹ are as defined above are novel, except for compounds in which A represents A¹ and R⁴ represents fluorine.

The formula (V) provides a general definition of the Grignard reagents furthermore used as starting materials for carrying out the process according to the invention. In this formula (V), Hal² preferably represents chlorine and R² has the preferred meanings below.

-   R² preferably represents hydrogen, fluorine, chlorine, bromine,     iodine, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl     or represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or     tert-butyl, each of which is mono- or polysubstituted by identical     or different substituents from the group consisting of fluorine,     chlorine and bromine. -   R² particularly preferably represents hydrogen, fluorine, chlorine,     bromine, methyl, ethyl, n- or isopropyl, n- or tert-butyl,     trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl,     dichloromethyl, chloromethyl, chlorofluoromethyl,     fluorodichloromethyl, difluorochloromethyl, pentafluoroethyl,     1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,     2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,     2-chloro-2,2-difluoroethyl, 2-dichloro-2-fluoroethyl,     2,2,2-trichloroethyl, 1-chlorobutyl, heptafluoro-n-propyl or     heptafluoroiso-propyl. -   R² very particularly preferably represents hydrogen, chlorine,     methyl, ethyl or trifluoromethyl.

The formula (VI) provides a general definition of the hydroxyalkylcarboxanilides which occur as intermediates when carrying out the process according to the invention. In this formula (VI), A, R¹ and R² have the preferred, particularly preferred, very particularly preferred and especially preferred meanings given above.

Some of the hydroxyalkylcarboxanilides of the formula (VI) are known and/or can be obtained by known processes (cf. WO 03/010149). Hydroxyalkylcarboxanilides of the formula (VI-a)

in which A, R¹ and R² are as defined above are novel, except for compounds in which A represents A1 and R⁴ represents fluorine.

The formula (VIIa) provides a general definition of the benzoxazines which furthermore occur as intermediates when carrying out the process according to the invention. In this formula (VIIa), A, R¹ and R² have the preferred, particularly preferred, very particularly preferred and especially preferred meanings given above.

Benzoxazines of the formula (VIIa) are novel. They also form part of this application and are obtained by steps one to three of the process according to the invention.

The formulae (VIIb) and (VIIc) provide a general definition of the alkenylanilides which furthermore occur as intermediates when carrying out the process according to the invention. In these formulae (VIIb) and (VIIc), A, R¹ and R² have the preferred, particularly preferred, very particularly preferred and especially preferred meanings given above.

Some of the alkenylanilides of the formulae (VIIb) and (VIIc) are known (cf. EP-A 0 824 099).

The first step of the process according to the invention can be carried out in the presence of an acid binder (a base) or else without acid binder (base), where the hydrochloric acid formed is given off on heating.

If a base is used, all customary inorganic or organic bases are suitable for carrying out the first step of the process according to the invention. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-amyloxide, potassium tert-amyloxide, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N-ethyldiisopropylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, picoline, ethylmethylpyridine, N-methylpiperidine, N-methylnorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). Particular preference is given to using potassium carbonate, sodium hydroxide, potassium hydroxide or pyridine.

Suitable diluents for carrying out the first step of the process according to the invention are all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofnn, 1,2-dimethoxyethane, 1,2-diethoxy-ethane or anisol; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; or sulphones, such as sulpholane; carboxylic acids, such as formic acid or acetic acid. Particularly preferably, the reaction is carried out in acetonitrile, N,N-dimethylformamide, N,N-di-methylacetamide, N-methylpyrrolidone, toluene or tetrahydrofuran.

When carrying out the first step of the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures of from −10° C. to +150° C.

When carrying out the first step of the process according to the invention, in general between 0.8 and 1.5 mol, preferably equimolar amounts, of the carbonyl halide of the formula (II) are employed per mole of the acetophenone derivative of the formula (III).

Depending on the reactivity of the starting materials, the reaction time may be up to 30 hours, but the reaction may be terminated earlier if complete conversion has been achieved.

The second step of the process according to the invention is carried out in aliphatic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, xylene, toluene, benzene or ethers, such as tetrahydrofuran, methyl tert-butyl ether, diethyl ether or in mixtures of the solvents mentioned, but preferably in toluene, if appropriate with addition of tetrahydrofuran, as diluent.

When carrying out the second step of the process according to the invention, the reaction temperatures may be varied within a relatively wide range. In general, the process is carried out at temperatures of from −30° C. to 50° C., preferably at temperatures of from −10° C. to 25° C.

When carrying out the second step of the process according to the invention, in general between 1.5 and 3 mol, preferably between 2 and 2.5 mol, of Grignard reagent of the formula (V) are employed per mole of the acetylanilide of the formula (IV). Part of the Grignard reagent may also be replaced by a base, such as, for example, a metal hydride; however, in this case at least 1 mol of Grignard reagent is required.

The second step of the process according to the invention is generally carried out using, as preferred solvent, toluene which is initially charged. The two starting materials [acetylanilide of the formula (IV) and Grignard reagent of the formula (V)] are then added to the solvent. In this manner, a conversion of more than 80% is achieved, whereas in the case of a customary practice of such a reaction (using tetrahydrofuran in which the starting material is dissolved, with subsequent addition of Grignard reagent) only 30% is achieved. By carrying out the reaction at relatively low temperatures, unwanted side reactions such as, for example, the exchange of halogens in the heterocyclic moiety for the Grignard alkyl group are reduced.

The elimination of water in the third step of the process according to the invention is carried out with acidic catalysis. Depending on the conditions, the benzoxazine and the isomeric pyrazolyl-alkenylanilides are obtained in varying compositions. However, the process according to the invention can also be implemented without carrying out the third step by subjecting the product of the second step directly to the conditions of the fourth step (hydrogenation).

Suitable diluents for carrying out the third step of the process according to the invention are all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-diethoxymethane, or anisol; alcohols, such as methanol, ethanol; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide or N-methylpyrrolidone; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; or sulphones, such as sulpholane; ketones, such as acetone or methyl isobutyl ketone; carboxylic acids, such as formic acid or acetic acid; or mixtures of these. Particularly preferably, the reaction is carried out in toluene, xylene, acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, methanol, ethanol or mixtures thereof.

The addition of water scavengers, such as orthoesters, molecular sieve or removal of the water formed by azeotropic distillation is also advantageous.

Suitable acids for carrying out the third step of the process according to the invention are, for example, p-toluenesulphonic acid, trifluoroacetic acid, sulphuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, or acid chlorides (such as, for example, POCl₃, SOCl₂, COCl₂).

The reaction is preferably carried out at from 60 to 140° C. or at the boiling point of the solvent using reaction times of from 1 h to 48 h, shorter reaction times favouring the formation of the benzoxazine longer reaction times favouring the pyrazolylalkenylanilides. Orthoesters are added, for example, in equimolar amounts, whereas the acids may be added in catalytic amounts of 0.1-20% by weight, preferably 1-10% by weight.

The fourth step of the process according to the invention is carried out in the presence of a catalyst. Suitable catalysts are all catalysts customarily used for hydrogenations. Raney nickel, palladium, palladium hydroxide, rhodium or platinum, if appropriate on a support, such as, for example, activated carbon, may be mentioned by way of example.

Suitable diluents for carrying out the fourth step of the process according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisol, or alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; acids, also in catalytic amounts, such as acetic acid, hydrochloric acid, hydrobromic acid, sulphuric acid, perchloric acid, trifluoroacetic acid; esters, such as methyl acetate, isopropyl acetate, ethyl acetate.

The process according to the invention is generally carried out under slightly elevated pressure. However, depending on the catalyst used and the temperature, it is also possible to operate under elevated or reduced pressure—in general between 0.1 bar and 50 bar, preferably between 1 bar and 10 bar.

The reaction temperature is in a range between 0 and 150° C., preferably between 20 and 100° C.

The reaction time is not critical and can be selected from a relatively large range of from 1 h to 40 h, preferably from 6 h to 24 h, depending on the batch size.

The alkylanilides of the formula (I) preparable by the process according to the invention are useful fungicides (cf. WO 03/010149).

The preparation according to the invention of alkylanilides of the formula (I) is described in the examples below, which further illustrate the above description. However, the examples are not to be interpreted in a limiting manner.

PREPARATION EXAMPLES Step 1: N-(2-Acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide From the Acid Chloride

With stirring at 0° C., a solution of 1,3-dimethyl-5-fluoro-4-pyrazolecarbonyl chloride (58.79 g, 333.3 mmol) in 170 ml of toluene is added dropwise to a solution of 2-aminoacetophenone (45 g, 333.3 mmol) in toluene (570 ml). The solution becomes turbid and is allowed to warm to room temperature. It is then boiled at reflux for 7 h, with evolution of HCl gas with foaming. The mixture is allowed to cool and the precipitated crystals are filtered off with suction after 12 h. The crystals are then stirred vigorously in 300 ml of sodium bicarbonate solution, filtered off with suction and washed with water. After drying, 82.6 g (90% of theory) of the target compound N-(2-acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide are obtained.

From the Acid Fluoride

A solution of 2-aminoacetophenone (405 mg, 3 mmol) and 1,3-dimethyl-5-fluoro-4-pyrazolecarbonyl fluoride (501 mg, 3 mmol) in toluene (7 ml) is boiled for 20 h, with addition of another 11% of the amount of pyrazole acid fluoride after 16 h. The hydrogen fluoride released is passed through dilute aqueous sodium hydroxide solution. The mixture is allowed to cool and the precipitated crystals are filtered off with suction after 12 h. They are then washed with toluene. After drying, 598 mg (65% of theory) of the target compound N-(2-acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide are obtained in a purity of 89% (GC).

Step 2: 5-Fluoro-N-[2-(1-hydroxy-1,3-dimethybutyl)phenyl]-1,3-dimethyl-1-H-pyrazole-4-carboxamide

Under argon and with stirring at −10° C., N-(2-acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (as a solid, 10 g, 36.3 mmol) and isobutylmagnesium chloride (as a 2 M solution in THF, 41.7 ml; 83.55 mmol) are added simultaneously and continuously to 400 ml of toluene over a period of 150 minutes. The mixture is allowed to warm to room temperature, 200 ml of ammonium chloride solution are added, the mixture is extracted three times with in each case 100 ml of ethyl acetate and the organic phases are dried using sodium sulphate and concentrated under reduced pressure. This gives 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (14.2 g, purity (GC/MS) 72.8%; 85% of theory) which still contains 14% of starting material.

Step 3: 2-(5-Fluoro-1,3-dimethyl-1H-pyrazol-4-yl)-4-isobutyl-4-methyl-4H-3,1-benzoxazine

The above product from step 2 is boiled in 150 ml of toluene with 0.2 g of p-toluenesulphonic acid on a water separator for 2 h. The mixture is washed with aqueous sodium bicarbonate solution and the organic phase is concentrated under reduced pressure. By stirring with heptane, it is possible to precipitate and remove by filtration the N-(2-acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide still present from the previous step. Chromatography gives 7.2 g (purity 85.1%; 63% of theory) of 2-(5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl)-4-isobutyl-4-methyl-4H-3,1-benzoxazine.

Variant with Trimethyl Orthoformate

14 g (80% pure, 33.6 mmol) of 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole carboxamide and 4.28 g (40.3 mmol) of trimethyl orthoformate are dissolved in 420 ml of toluene, and 5 drops of concentrated sulphuric acid are added. The solution is boiled for 1 h, treated with sodium sulphate and filtered off, and the filtrate is concentrated under reduced pressure. The residue is treated with 300 ml of heptane. This results in the N-(2-acetylphenyl)-5-fluoro-1,3-dimethyl-1H-pyrazolecarboxamide still present in the starting material precipitating out. The filtrate is concentrated using a rotary evaporator, giving 10.7 g of a yellow oil. Examination by GC/MS shows the following composition: 24% A, 25% B, 29% C and 7% of a methanol adduct.

Variant with Longer Reaction Time

5-Fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (70 g, purity 99%, 208 mmol) is boiled in 1.4 l of toluene with p-toluenesulphonic acid (2 g) on a water separator for 40 hours. The mixture is washed with 50 ml of aqueous sodium bicarbonate solution and the organic phase is concentrated under reduced pressure. This gives 64.3 g of an oil which, according to GC/MS, consists of 18% 5-fluoro-1,3-dimethyl-N-[2-(3-methyl-1-methylenebutyl)phenyl]-1H-pyrazole-4-carboxamide and 18 and 58%, respectively, of N-{2-[(1Z and E)-1,3-dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide. N-{2-[1,3-Dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide: ¹H-NMR (400 MHz; CDCl₃): δ=1.05 (d, 6H, 2CH3), 1.95 (s, 31, CH3); 3.72 (s, 3H, CH3), 5.32 (d, 1H, C═C—H), 7.05 (m, 2H), 7.25 (m, 1H); 7.76 (s, 1H, NH), 8.31 (d, 1H)

Step 4: N-[2-(1,3-Dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide

Hydrogenation of the Benzoxazine

1 g of 2-(5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl)-4-isobutyl-4-methyl-4H-3,1-benzoxazine in 30 ml of glacial acetic acid is hydrogenated with 250 mg of Pd—C (50% in water) in an autoclave at room temperature under a hydrogen pressure of 2 bar for 5 h. The mixture is filtered off with suction through Celite, the filter cake is washed with ethyl acetate and the filtrate is concentrated under reduced pressure. The residue obtained in this manner is taken up in ethyl acetate, washed with water, dried and concentrated using a rotary evaporator. The residue is then taken up in heptane and again concentrated under reduced pressure, and the resulting clear oil is dried under reduced pressure. The oil begins to crystallize (1.05 g).

GC/MS: 82.6% of N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Hydrogenation of the Mixture of Benzoxazine and Pyrazolylalkenylanilides

At room temperature and under a hydrogen pressure of 20 bar, 10 g of the mixture of 24% A, 25% B, 29% C are prehydrogenated in 150 ml of glacial acetic acid using 350 mg of 10% Pd on carbon for 5 minutes. This mixture is added to a suspension of 1.38 g of Pd on carbon (10%) which was also prehydrogenated at 20 bar for 5 minutes. The combined mixture is then hydrogenated at room temperature and a hydrogen pressure of 5 bar for 5 hours. The mixture is filtered off with suction through Celite, the filter cake is washed with ethyl acetate and the filtrate is concentrated under reduced pressure. The residue obtained in this manner is taken up in ethyl acetate, washed with saturated sodium bicarbonate solution, dried and concentrated using a rotary evaporator. This gives a crystallizing oil (9.39 g).

GC/MS: 75.6% of N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Hydrogenation of N-{2-[(1Z and E)-1,3-dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide

1 g (82% pure, 2.6 mmol) of N-{2-[(1Z and E)-1,3-dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide is dissolved in 30 ml of methanol, and 100 mg of 10% palladium on carbon is added. The mixture is hydrogenated in an autoclave at a hydrogen pressure of 50 bar and at 40° C. for 19 hours. The catalyst is filtered off through Celite and the solution is concentrated under reduced pressure.

This gives 0.9 g of a crystallizing oil.

Content (GC-MS): 88.9% (97% of theory) of N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Hydrogenation of N-{2-[(1Z and E)-1,3-dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide

12 g (92.2% pure, 35 mmol) of N-{2-[(1Z and E)-1,3-dimethylbut-1-en-1-yl]phenyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (isomer ratio 18:65; contains 8% of the exo-compound) are dissolved in 120 ml of methanol, with 600 mg of 10% palladium on carbon and 2.3 g (contains 15.2 mmol of acid) of a mixture of 5 ml of concentrated sulphuric acid and 5 ml of water are added and the mixture is hydrogenated at a hydrogen pressure of 5 bar and at 21° C. for 24 hours. The catalyst is filtered off with suction through Celite and the filter cake is washed with ethyl acetate. The filtrate is concentrated, the residue is taken up in ethyl acetate and washed with saturated sodium bicarbonate solution and the organic phase is separated off and concentrated. This gives 11.1 g of beige crystals. Content (GC-MS): 93.9% (93.6% of theory) of N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Hydrogenation of 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide

0.6 g of mixture of 5 ml of concentrated sulphuric acid and 5 ml of water are added to 40 ml of tetrahydrofuran. 2 g (99% pure, 5.95 mmol) of 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide and 50 mg of palladium hydroxide on carbon (Pd content 20%) are added, and the mixture is hydrogenated at a hydrogen pressure of 5 bar and at 90° C. for a total of 16 hours. The catalyst is filtered off with suction through Celite and the filter cake is washed with ethyl acetate. The filtrate is concentrated, the residue is taken up in ethyl acetate and washed with saturated sodium bicarbonate solution and the organic phase is separated off and concentrated. This gives 1.8 g of white crystals.

Content (GCMS): 98.2% (93.6% of theory) of N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide.

Hydrogenation of 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide

40 g (99.2% pure, 119 mmol) of 5-fluoro-N-[2-(1-hydroxy-1,3-dimethylbutyl)phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide in 400 ml of 2-methyltetrahydrofuran are hydrogenated with 3.63 g of a 64 percent strength (w/w) sulphuric acid and 1 g of 10% Pd/C at a hydrogen pressure of 5 bar and at 80° C. for 16 hours.

The mixture is filtered off with suction through Celite, the filter cake is washed with 100 ml of 2-methyltetrahydrofuran, the filtrate is washed with 20 ml of saturated sodium bicarbonate solution and the organic phase is concentrated under reduced pressure. The residue is dissolved in 30 ml of toluene at 60° C., cooled to 0° C. with stirring, filtered off with suction and washed with 20 ml of ice-cold toluene. This gives 33.2 g (87% of theory) of beige N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide crystals of melting point 111-113° C., purity 98.8% (GC against standard). 

1. A process for preparing alkylanilides of the formula (I)

in which R¹ represents hydrogen or fluorine, R² represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 9 fluorine, chlorine and/e or bromine atoms; A represents the radical of the formula (A1)

in which R³ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl, R⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, and R⁵ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having in each case 1 to 5 halogen atoms, or phenyl, or A represents the radical of the formula (A2)

in which R⁶ and R⁷ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R⁸ represents halogen, cyano, C₁-C₄-alkyl, or C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A3)

in which R⁹ and R¹⁰ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R¹¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A4)

in which R¹² represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A5)

in which R¹³ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, and R¹⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl, or A represents the radical of the formula (A6)

in which R¹⁵ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R¹⁶ represents C₁-C₄-alkyl, Q¹ represents S (sulphur), O (oxygen), SO, SO₂ or CH₂, and p represents 0, 1 or 2, where R¹⁶ represents identical or different radicals if p represents 2, or A represents the radical of the formula (A7)

in which R¹⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A8)

in which R¹⁸ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A9)

in which R¹⁹ and R²⁰ independently of one another represent hydrogen, halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A10)

in which R²² and R²³ independently of one another represent hydrogen, halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁴ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A11)

in which R²⁵ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁶ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A12)

in which R²⁷ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁸ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A13)

in which R²⁹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A14)

in which R³⁰ represents hydrogen or C₁-C₄-alkyl, and R³¹ represents halogen or C₁-C₄-alkyl, or A represents the radical of the formula (A15)

in which R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 16)

in which R³³ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A17)

in which R³⁴ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A 18)

in which R³⁵ represents hydrogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl having 1 to 5 halogen atoms, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl, di(C₁-C₄-alkyl)aminosulfonyl, C₁-C₆-alkylcarbonyl or in each case optionally substituted phenylsulfonyl or benzoyl, R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁷ represents hydrogen, halogen, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R³⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A19)

in which R³⁹ represents C₁-C₄-alkyl, comprising: a) reacting a carbonyl halide of the formula (II)

in which A is a radical of formulae (A1), (A2), (A3), (A4), (A5), (A6), (A7), (A8), (A9), (A10), (A11), (A12), (A13), (A14), (A15), (A16), (A17), (A18), or (A19) defined above, and Hal¹ represents fluorine, chlorine or bromine, reacted with an acetophenone derivative of the formula (III) or a salt thereof

in which R¹ is hydrogen or fluorine, optionally in the presence of an acid binder and optionally in the presence of a diluent, to give an acetylanilide of the formula (IV)

in which A and R¹ are as defined above, b) reacting a compound of formula (IV) with a Grignard reagent of the formula (V)

in which R² is hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 9 fluorine, chlorine or bromine atoms, and Hal² represents chlorine, bromine or iodine, in the presence of a diluent, to give a hydroxyalkylcarboxanilide of the formula (VI)

in which R¹, R² and A are as defined above, and c1) hydrogenating a compound of formula (VI) in the presence of a catalyst and in the presence of a diluent and an acid, to give a compound of formula (I); or c2) reacting a compound of formula (VI) in the presence of an acid and in the presence of a diluent, d) to give a benzoxazine of the formula (VIIa) and an alkenylanilide of the formulae (VIIb) and (VIIc)

in which R¹, R² and A are as defined above, and d) hydrogenating a compound of formula (VIIa), (VIIb) or (VIIc) in the presence of a catalyst, optionally in the presence of an acid and in the presence of a diluent, to give a compound of formula (I).
 2. The process of claim 1, wherein b) is carried out in toluene, toluene/tetrahydrofuran mixtures or toluene/methyl tert-butyl ether mixtures.
 3. The process of claim 1 wherein in b) the solvent is initially charged and during the reaction a compound of formula (IV) and a compound of formula (V) are metered in simultaneously.
 4. The process of claim 1, wherein said compound of formula (II) is 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl chloride or 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl fluoride, said compound of formula (III) is 2-aminoacetophenone and said compound of formula (V) is isobutylmagnesium chloride and the product obtained is N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazol-4-carboxamide.
 5. A compound of formula (IV-a)

in which R¹ represents hydrogen or fluorine, A represents the radical of the formula (A1)

in which R³ represents hydrogen, cyano, halogen, nitro, C₁-C_-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl C₁-C₄-haloalkyl C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl R⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, and R⁵ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having in each case 1 to 5 halogen atoms, or phenyl, or A represents the radical of the formula (A2)

in which R⁶ and R⁷ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R⁸ represents halogen, cyano, C₁-C₄-alkyl, or C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A3)

in which R⁹ and R¹⁰ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R¹¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A4)

in which R¹² represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A5)

in which R¹³ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, and R¹⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy. C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl. or A represents the radical of the formula (A6)

in which R¹⁵ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R¹⁶ represents C₁-C₄-alkyl, Q¹ represents S (sulphur), O (oxygen), SO, SO₂ or CH₂, and p represents 0, 1 or 2, where R¹⁶ represents identical or different radicals if p represents 2, or A represents the radical of the formula (A7)

in which R¹⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms. or A represents the radical of the formula (A8)

in which R¹⁸ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A9)

in which R¹⁹ and R²⁰ independently of one another represent hydrogen, halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 10)

in which R²² and R²³ independently of one another represent hydrogen, halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁴ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A11)

in which R²⁵ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁶ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A12)

in which R²⁷ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁸ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 13)

in which R²⁹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A14)

in which R³⁰ represents hydrogen or C₁-C₄-alkyl, and R³¹ represents halogen or C₁-C₄-alkyl, or A represents the radical of the formula (A15)

in which R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 16)

in which R³³ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 17)

in which R³⁴ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A18)

in which R³⁵ represents hydrogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl having 1 to 5 halogen atoms, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl, di(C₁-C₄-alkyl)aminosulfonyl, C₁-C₆-alkylcarbonyl or in each case optionally substituted phenylsulfonyl or benzoyl, R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁷ represents hydrogen, halogen, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R³⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms. or A represents the radical of the formula (A 19)

in which R³⁹ represents C₁-C₄-alkyl, with the proviso that when A is A1, R⁴ is not fluorine.
 6. A compound of formula (VI-a)

in which R¹ represents hydrogen or fluorine, R² represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 9 fluorine, chlorine or bromine atoms, A represents the radical of the formula (A1)

in which R³ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl, R⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, and R⁵ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having in each case 1 to 5 halogen atoms, or phenyl, or A represents the radical of the formula (A2)

in which R⁶ and R⁷ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R⁸ represents halogen, cyano, C₁-C₄-alkyl, or C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A3)

in which R⁹ and R¹⁰ independently of one another represent hydrogen, halogen C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R¹¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A4)

in which R¹² represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl. C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A5)

in which R¹³ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, and R¹⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl, or A represents the radical of the formula (A6)

in which R¹⁵ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R¹⁶ represents C₁-C₄-alkyl. Q¹ represents S (sulphur), O (oxygen), SO, SO₂ or CH₂, and p represents 0, 1 or 2, where R¹⁶ represents identical or different radicals if p represents 2, or A represents the radical of the formula (A7)

in which R¹⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A8)

in which R¹⁸ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A9)

in which R¹⁹ and R²⁰ independently of one another represent hydrogen, halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²¹ represents hydrogen halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having-1 to 5 halogen atoms, or A represents the radical of the formula (A10)

in which R²² and R²³ independently of one another represent hydrogen, halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁴ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A11)

in which R²⁵ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁶ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A12)

in which R²⁷ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁸ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 13)

in which R²⁹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A14)

in which R³⁰ represents hydrogen or C₁-C₄-alkyl, and R³¹ represents halogen or C₁-C₄-alkyl, or A represents the radical of the formula (A 15)

in which R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 16)

in which R³³ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 17)

in which R³⁴ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A18)

in which R³⁵ represents hydrogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl having 1 to 5 halogen atoms, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl, di(C₁-C₄-alkyl)aminosulfonyl, C₁-C₆-alkylcarbonyl or in each case optionally substituted phenylsulfonyl or benzoyl, R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁷ represents hydrogen, halogen, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R³⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms. or A represents the radical of the formula (A 19)

in which R³⁹ represents C₁-C₄-alkyl. with the proviso that when A is A1, R⁴ is not fluorine;
 7. A compound of formula (VIIa)

in which R¹ represents hydrogen or fluorine, R² represents hydrogen halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 9 fluorine, chlorine or bromine atoms; A represents the radical of the formula (A1)

in which R³ represents hydrogen, cyano, halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, aminocarbonyl or aminocarbonyl-C₁-C₄-alkyl, R⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, and R⁵ represents hydrogen, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₃-C₆-cycloalkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl having in each case 1 to 5 halogen atoms, or phenyl, or A represents the radical of the formula (A2)

in which R⁶ and R⁷ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R⁸ represents halogen, cyano, C₁-C₄-alkyl, or C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A3)

in which R⁹ and R¹⁰ independently of one another represent hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R¹¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A4)

in which R¹² represents hydrogen, halogen, hydroxyl, cyano, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A5)

in which R¹³ represents halogen, hydroxyl, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, and R¹⁴ represents hydrogen, halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl, or A represents the radical of the formula (A6)

in which R¹⁵ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R¹⁶ represents C₁-C₄-alkyl, Q¹ represents S (sulphur), O (oxygen), SO, SO₂ or CH₂, and p represents 0, 1 or 2, where R¹⁶ represents identical or different radicals if p represents 2, or A represents the radical of the formula (A7)

in which R¹⁷ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A8)

in which R¹⁸ represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A9)

in which R¹⁹ and R²⁰ independently of one another represent hydrogen, halogen, amino, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²¹ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A10)

in which R²² and R²³ independently of one another represent hydrogen halogen, amino, nitro, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁴ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A11)

in which R²⁵ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁶ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 12)

in which R²⁷ represents hydrogen, halogen, amino, C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R²⁸ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A13)

in which R²⁹ represents halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A14)

in which R³⁰ represents hydrogen or C₁-C₄-alkyl, and R³¹ represents halogen or C₁-C₄-alkyl, or A represents the radical of the formula (A15)

in which R³² represents C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A16)

in which R³³ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A 17)

in which R³⁴ represents halogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkylthio or C₁-C₄-haloalkoxy having in each case 1 to 5 halogen atoms, or A represents the radical of the formula (A18)

in which R³⁵ represents hydrogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl having 1 to 5 halogen atoms, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl, di(C₁-C₄-alkyl)aminosulfonyl, C₁-C₆-alkylcarbonyl or in each case optionally substituted phenylsulfonyl or benzoyl, R³⁶ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, R³⁷ represents hydrogen, halogen, cyano, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, and R³⁸ represents hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl having 1 to 5 halogen atoms, or A represents the radical of the formula (A19)

in which R³⁹ represents C₁-C₄-alkyl.
 8. The process of claim 2, wherein in b) the solvent is initially charged and during the reaction a compound of formula (IV), preferably in solid form, and a compound of formula (V) are metered in simultaneously.
 9. The process of claim 2, wherein said compound of formula (II) is 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl chloride or 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl fluoride, said compound of formula (III) is 2-aminoacetophenone, and said compound of formula (V) is isobutylmagnesium chloride, and the product obtained is N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazol-4-carboxamide.
 10. The process of claim 3, wherein said compound of formula (II) is 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl chloride or 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl fluoride, said compound of formula (III) is 2-aminoacetophenone, and said compound of formula (V) is isobutylmagnesium chloride, and the product obtained is N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazol-4-carboxamide.
 11. The process of claim 8, wherein said compound of formula (II) is 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl chloride or 1,3-dimethyl-5-fluoro-4-pyrazolcarbonyl fluoride, said compound of formula (III) is 2-aminoacetophenone, and said compound of formula (V) is isobutylmagnesium chloride, and the product obtained is N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazol-4-carboxamide.
 12. The process of claim 3, wherein said compound of formula (IV) is in solid form. 